Coordination polymers with carborane anions: silver dinitrile complexes

Crystalline materials have been isolated and characterized from mixing the silver carborane salts Ag(CB(11)H(12)) or AgCo(C(2)B(9)H(11))(2)] with nitrile ligands, either terminal acetonitrile or potentially bridging alkanedinitriles. Most of the complexes showed B-H...Ag interactions between the silver center and carborane anion. Ag(acetonitrile)(2)(CB(11)H(12))] has a hexagonal network structure. Ag(malonitrile)(2)(CB(11)H(12))] is a discrete dimeric complex, while Ag(4)(succinonitrile)(5)(CB(11)H(12))(4)], Ag(glutaronitrile)(2)]Co(C(2)B(9)H(12))(2)], and Ag(glutaronitrile)Co(C(2)B(9)H(11))(2)]] all show coordination chain structures. The carborane anions in Ag(adiponitrile)Co(C(2)B(9)H(11))(2)]] bridge between Ag centers to give a 3D CdSO(4)-related coordination polymer. The structure of Ag(malonitrile)(2)](BF(4)) was also determined to have an unusual chiral diamondoid structure with a skewed 2-fold interpenetration.